Method of increasing the SPF rating and compounds suitable for increasing the SPF rating of fibre or fabric

ABSTRACT

The present invention provides a method of increasing the sun protection factor (SPF) rating of a fiber or fabric, comprising the steps of providing a UVR absorber, applying the UVR absorber to a fabric, whereby the UVR absorber is attached to the fiber and an application of less than 3% UVR absorber on weight of fiber produces an SPF rating of greater than 20 for the UVR absorber and fabric combination.

TECHNICAL FIELD

The present invention relates to a method of increasing the sunprotection factor (SPF) rating and compounds suitable for increasing theSPF rating of fibre or fabric.

BACKGROUND OF THE INVENTION

Last year over 1,000 Australians died of skin cancer while two thirds ofthe Australian population will develop some form of skin cancer at somestage in their lives. This year it is anticipated that 150,000Australians will go to their doctors for the examination and treatmentof some form of sun induced skin cancer.

It is interesting to note that, in spite of public education campaignsand the widespread use of "Sun-Block" creams, skin cancer rates have notchanged in recent years.

Even though there has been various sun protection aids in the market formany years, the present inventors have found that most consumers do notfully understand what an SPF rating means.

A typical fair skinned person, on a summers day in Australia, at noon(1:00 pm Eastern Summer Time), would "burn" in approximately 15 minutes(i.e. 0.25 hours). If this person applied "sun block" cream (or textile)of SPF 4 (if available), then this person would burn in 4 times 15minutes, viz 1 hour. It is important to note, however, that this personwould have received the same total UVR dose either way.

A common way of avoiding sunburn when performing activities in a sunnyenvironment is to apply a sunburn cream to skin. The problem with such asolution however is that most sunburn creams only provide UVR protectionup to an SPF rating of 15+ and therefore prolonged exposure to the suncan still cause damage to a persons skin despite the use of a sunburncream.

In addition, avoiding exposure of skin to the sun by wearing clothing,for example a T-shirt, does not necessarily provide adequate UVRprotection for the wearer, when the wearer is exposed to the sun forprolonged periods. This problem is compounded by the fact that in hotclimates it is desirable to have light weight clothing, which typicallyhas a low SPF rating.

For example, for materials having a density of less than 200 grams persquare meter, nylon has an SPF rating of between 10 and 15, polyesterhas an SPF rating of between 13 and 17, wool has an SPF rating of 10-20and cotton has an SPF rating of between 5 and 15. It follows thereforethat a person wearing a shirt made of light weight fabric such as cottonor wool, if exposed to the sun for prolonged periods can still besubjected to significant doses of UVR radiation. Thus, over an extendedperiod of time, a person working in the sun and wearing a cotton T-shirtcan still be exposed to a significant cumulative dose of UVR radiation.

Essentially, the SPF protection of a fabric depends on the "CoverFactor" of the fabric. The Cover Factor may be defined as the percentageof the fabric surface that is covered by the yarns of the fabric. If oneassumes that the yarns employed to weave or knit the fabric arecompletely opaque to UVR radiation (which is not the case in reality)then the fabric SPF would be simply related to Cover Factor by thefollowing formula: ##EQU1##

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a graph of the UV-transmission of a 5 g/L ethanol solution ofthe compound of Example 1 as measured in a 5 mm quartz cell in a Cary 3UV-visible spectrophotometer.

DISCLOSURE OF THE INVENTION

In one aspect, the present invention provides a method of increasing theSPF rating of a fibre or fabric, comprising the steps of providing a UVRabsorber, applying the UVR absorber to a fabric having a density of lessthan 200 grams per square meter, whereby the UVR absorber is attached tothe fibre and an application of less than 3% UVR absorber on weight offibre produces an SPF rating of greater than 20 for the UVR absorber andfabric combination.

In one embodiment, the present invention provides a method of increasingthe SPF rating of a fibre or fabric, comprising the steps of providing aUVR absorber, applying the UVR absorber to a fabric having a density ofless than 200 grams per square meter, whereby the UVR absorber isattached to the fibre and an application of less than 2% UVR absorber onweight of fibre produces an SPF rating of greater than 20 for the UVRabsorber and fabric combination.

Preferably the UVR absorber enters the fibre and fixes itself to thefibre.

It is preferred that the combination of fabric and UVR absorber iswater-fast so that washing of the fabric after its SPF rating has beenincreased by the addition of the UVR absorber, does not cause anysignificant drop in the SPF rating of the fibre.

Preferably the UVR absorber comprises a substituted benzotriazole.

The fibre may be wool, nylon, polyester, cotton or any other syntheticfibre or composite thereof.

It is preferred that when the fibre is nylon the UVR absorber is Fadex F(registered trade name of Sandoz).

It is preferred that when the fibre is polyester, the UVR absorber isFadex F (registered trade name of Sandoz).

Preferably the SPF rating is increased by greater than 30 fornon-composite fabrics and by greater than 9 for composite fabrics.

It is preferred that when the fibre is wool the UVR absorber is CIBAFASTW (registered trade name of CIBA-GEIGY).

It is preferred that when the fibre is a secondary cellulose acetate ortriacetate, the UVR absorber is Fadex F (registered trade name ofSandoz).

In a second aspect, the present invention provides a method ofincreasing the SPF rating of cellulosic or protein fibre or fabric,comprising applying to cellulosic or protein fibre or fabric one or morecompounds of formula (I)-(IV): ##STR1## wherein A is --NH-- or --SO₂ --and when A is --NH--, B is selected from a compound of formula (i)-(vii)as follows: ##STR2## and where A is --SO₂ --, B is selected from acompound of formulae (viii)-(x) as follows:

(viii) --CH═CH--OSO₃ H

(ix) --CH₂ --CH₂ --OSO₃ H

(x) --NH--CH₂ --CH₂ --OSO₃ H

wherein R is independently selected from --OH,--NH₂,--SO₃ ⁻ M⁺, --SO₃ H,alkyl, alkoxy, alkanoyl, alkylcarboxylate, --S--alkyl, --CF₃,--N-di-alkyl;

n=0, 1, 2, 3 or 4

M⁺ =cation

X=H, or Cl, F, Br and is independently selected

Y=X or R.

In a third aspect, the present invention provides a compound of formula(I), (II), (III) or (IV) ##STR3## wherein A, B, R and n are as definedabove; but excluding the compound of formula (III) where A is --NH--, Bis a compound of formula (ii);

X is Cl, n is 2 and one R is in the 3-position of the phenyl ring and is--CH₃ and the other R is in the 4-position and is --SO₃ ⁻ Na⁺.

In a fourth aspect, the present invention provides a process ofpreparing a compound of formula (I)-(IV) which comprises:

1) for preparing compounds of formula (I)-(IV) where A is --NH-- and Bis a compound of formula (i), (ii), (iii), (iv) or (v): reacting theappropriate amine of formula (I), (II), (III) or (IV) with a chloroderivative of a compound of formula (i), (ii), (iii), (iv) or (v);

2) for preparing compounds of formula (I)-(IV) wherein A is --NH-- and Bis a compound of formula (vi) or (vii):

(i) reacting the appropriate amine of formula (I), (II), (III) or (IV)with --CH₂ BrCHBrCOCl to provide the dibromopropionyl derivative;

(ii) debromination with potassium hydroxide or the like to provide thebromoacrylamido derivative of formula (vi); and

(iii) further debromination with potassium hydroxide or the like toprovide the acrylamido derivative of formula (vii);

3) for preparing compounds of formula (I)-(IV) where A is --SO₂ -- and Bis a compound of formula (viii) or (ix):

(i) esterification of the appropriate B-hydroxethyl sulphone derivativesof the compounds of formulae (I) to (IV) with sulphuric acid or the liketo provide compounds of formula (I) to (IV) where B is a compound offormula (viii) and;

(ii) dehydration in the presence of a base to form the vinyl compound offormula (ix);

4) for preparing compounds of formula (I)-(IV) where A is --SO₂ -- and Bis a compound of formula (x):

esterification of the appropriate B-hydroxyethyl aminosulphonederivative of the compounds of formulae (I)-(IV) with sulphuric acid orthe like (as in 3(i) above) to provide compounds of formula (I)-(IV)where B is a compound of formula (x).

Preferred compounds of formula (I)-(IV), designated as P-Q forconvenience combination of P with any Q as follows: ##STR4##

The starting materials for the above processes 1 to 4 are knowncompounds and are readily available. Given the compounds to be reacted,the skilled addressee would be able to readily determine the reactionconditions.

Compounds of formulae (I)-(IV) are useful as UVR absorber compounds andcan be applied to fabrics of any weight. Typically, they are suitablefor application to light weight summer fabrics and to heavier fabric upto and including industrial weight fabrics.

In a fifth aspect, the present invention provides a method of increasingthe SPF rating of cellulosic or protein fibre or fabric, comprising thesteps of applying a compound of formula (I)-(IV) to cellulosic orprotein fibres or fabric having a density of less than 200 g/m² wherebyan application of less than 3% of a compound of formula (I)-(IV) onweight of fibre or fabric produces an SPF rating of greater than 20.

In another embodiment, the present invention provides a method ofincreasing the SPF rating of cellulosic or protein fibre or fabric,comprising the steps of applying a compound of formula (I)-(IV) tocellulosic or protein fibres or fabric having a density of less than 200g/m² whereby an application of less than 2% of a compound of formula(I)-(IV) on weight of fibre or fabric produces an SPF rating of greaterthan 20.

Cellulosic fibres may be any fibres of plant origin such as cotton,viscose, flax, linen, rayon or the like or composites thereof. Also,composites can be with polyester, polyamides, polyacrylonitriles or thelike.

Protein fibres may be any fibres of animal origin such as wool, mohair,silk, cashmere, angora or the like or composites thereof. Also,composites can be with polyester, polyamide or the like.

It is preferred that when the fibre is protein, a compound of formula(I)-(IV) where B is (ii), (iv), (v), (vi), (vii), (viii) or (ix) isapplied.

It is preferred that when the fibre is cellulosic, a compound of formula(I)-(IV) where B is (i), (ii), (iii) or (iv) is applied.

Preferably, the cellulosic fibre is cotton and the protein fibre iswool.

Typically, a 2% on weight of fibre application of compound of formula(III) will increase the SPF rating of a 120 g/m² 100% cotton fabric from15+ to 30+.

Typically, a compound of formula (I)-(IV) enters the fibre and fixesitself to the fibre with the reactive group B of compounds of formula(I)-(IV) reacting with the fibre.

Typically, for composite fabrics, sequential application of UVR absorberrelevant for each component of the composite increases the SPF rating ofthe composite fabric by greater than 30.

For example, for cotton/polyester fabric, sequential application of UVRabsorber for cotton followed by the application of UVR absorber forpolyester or vice versa, increases the SPF rating of the fabric bygreater than 30.

In a sixth aspect, the present invention provides an article of clothingcomprising a plurality of fibres and a UVR absorber, wherein theplurality of fibres have a density of less than 200 grams per squaremeter and the SPF rating of the article has been increased to at least20 by the addition of less than 3% UVR absorber on weight of fibre.

Preferably, in the article of clothing comprising a plurality of fibresand a UVR absorber, wherein the plurality of fibres have a density ofless than 200 grams per square meter, the SPF rating of the article hasbeen increased to at least 20 by the addition of less than 2% UVRabsorber on weight of fibre.

According to another aspect of the present invention, there is providedan article of clothing comprising a plurality of fibres and a UVRabsorber of compound of formula (I)-(IV).

Preferably, in the article of clothing with the UVR absorber ofcompounds of formula (I)-(IV), the plurality of fibres has a density ofless than 200 g/m².

Preferably, in the article of clothing with the UVR absorber compound offormula (I)-(IV) wherein the plurality of fibres have a density of lessthan 200 g/m², the SPF rating of the article has been increased to atleast 20 by the addition of less than 3% UVR absorber on weight offibre.

More preferably, in the article of clothing with the UVR absorbercompound of formula (I)-(IV) wherein the plurality of fibres have adensity of less than 200 g/m², the SPF rating of the article has beenincreased to at least 20 by the addition of less than 2% UVR absorber onweight of fibre.

Preferably, the fibre comprising the UVR absorber is colour-fast andlight-fast.

Typically, the UVR absorber is bonded to the fibre by virtue of thereaction of compounds of formula (I)-(IV) with the fibre.

The present invention also provides a formulation suitable forapplication to cellulosic or protein fibres or fabrics comprising acompound of formula (I)-(IV) in a suitable carrier.

Preferably, the SPF rating is increased to greater than 30.

It is preferred that the combination of fibre or fabric and UVR absorberis water-fast so that washing of the fabric after its SPF rating hasbeen increased by the addition of the UVR absorber compounds of formula(I)-(IV), does not cause any significant drop in the SPF rating of thefibre or fabric.

The fibre or fabric may also comprise a dye or pigment or other coatingsor finishes known in the industry.

It is preferred that the UVR absorber be transparent to visibleradiation when applied to the fibre or fabric. Typically, once appliedthe original colour of the fabric or fibre is substantially unaffected.

The combination of fabric and UVR absorber is preferably light-fast. Thefibre or fabric treated with the UVR absorber is preferably colour-fastto washing.

The fibre my be wool, nylon, polyester, cotton or any other syntheticfibre or composite thereof.

Preferably the UVR absorber is bonded to the fibres by virtue of anaffinity the UVR absorber has for the fibres.

Preferred embodiments of the present invention will now be described byway of example only with reference to the accompanying experimentalresults.

BEST MODES FOR CARRYING OUT THE INVENTION

SYNTHESIS METHODS

Example 1

Synthesis via 1,3,5-s-triazine (cyanuric chloride)

The selected amine compound (1 mole as a slurry in 100 ml water [icecold]) is added slowly to cyanuric chloride (1 mole as a slurry in 200ml acetone [ice cold]), whilst maintaining the pH of the solution at 7by the addition of 2N sodium hydroxide. The reaction mixture is stirredfor 1.5-2.0 hours (whilst maintaining the temperature below 5° C.) afterwhich time the reaction is judged to be complete once the pH stabilisesat 7 and the test for free amine (TLC) is negative. The product is thenfiltered off, washed thoroughly with acetone and then oven dried.

Example 2

Synthesis via 2,4,6-trifluoro-5-chloro-pyrimidine

The selected amine compound (1 mole as a slurry in 100 ml water [icecold]) is added slowly to 2,4,6-trifluoro-5-chloro-pyrimidine (1 moledissolved in 300 ml acetone [ice cold]), whilst maintaining the pH ofthe solution at 7 by the addition of a saturated aqueous solution ofsodium carbonate. The reaction mixture is stirred for 1.5-2.0 hours(whilst maintaining the temperature below 5° C.) after which time thereaction is judged to be complete once the pH stabilises at 7 and thetest for free amine (TLC) is negative. The product is then filtered off,washed thoroughly with acetone and then oven dried.

Example 3

Synthesis via epichlorohydrin

The selected amine compound (1 mole as a slurry in 100 ml ethanol [icecold]) is added slowly to epichlorohydrin (1 mole dissolved in 100 mlethanol [ice cold]), whilst maintaining the pH of the solution at 7 bythe addition of a saturated aqueous solution of sodium carbonate. Thereaction mixture is stirred for 1.5-2.0 hours (whilst maintaining thetemperature below 5° C.) after which time the reaction is judged to becomplete once the pH stabilises at 7 and the test for free amine (TLC)is negative. The product is then filtered off, washed thoroughly withacetone and then oven dried.

Example 4

Synthesis via 2,3-dibromopropionic acid chloride

2,3-dibromopropionic acid chloride (1 mole) is added dropwise to asolution of the selected amine (1 mole as a slurry in 100 ml acetonecontaining 0.5 mole pyridine) at 30°-45° C. The reaction mixture is thenstirred for 14 hours at room temperature. The pyridine and acetonesolvents are then removed by vacuum evaporation.

The intermediate 2,3-dibromopropionamide compound:

    [A]--NHCO--CHBrCH.sub.2 Br

is then treated as follows:

1 mole of the 2,3-dibromopropionamide compound is charged into 500 mlethanol and heated to 60° C. Then add dropwise a solution consisting of1.6 mole of potassium hydroxide in 250 ml ethanol. The temperature ofthe reaction vessel is then raised from 60° to 68° C. Upon completion ofthe addition, the reaction mixture is heated under reflux for 4 hours.

Example 5

Synthesis of 2,4-dichloro-s-triazin-6-yl-p-aminophenyl-sulphonic acidsodium salt (dihydrate)

p-aminophenyl-sulphonic acid (sulphanilic acid) (26 g as a slurry inwater) was added slowly to cyanuric chloride (28 g as a slurry in 200 mlacetone containing circa 100 g ice), whilst maintaining the pH of thesolution at 7 by the addition of 2N sodium hydroxide. The reactionmixture was stirred for 1.5-2.0 hours after which time the reaction wasjudged to be complete once the pH had stabilised at 7 and the test forfree amine (TLC) was negative. The product was filtered off, washedthoroughly with acetone and then oven dried. The yield was 92%.

TLC showed that the product was free of starting materials. The IRspectrum and elemental analysis results confirmed the authenticity ofthe product. The elemental analysis results are given in the followingtable.

    ______________________________________                                               Carbon     Hydrogen  Nitrogen                                          ______________________________________                                        Expected 27.40        1.72      21.30                                         Found    27.53        1.84      21.25                                         ______________________________________                                    

Example 6

Synthesis of2,4-dichloro-s-triazin-6-yl-amino-8-naphthol-3,6-disulphonic acid sodiumsalt (dihydrate)

38 g 1-amino-8-naphthol-3,6-disulphonic acid was dissolved in 1N sodiumbicarbonate solution, the solution was diluted to 500 ml and neutralisedwith acetic acid. This solution and 2N sodium bicarbonate solution weredropped simultaneously into a well stirred suspension of cyanuricchloride (20.2 g) in acetone and ice water (100 ml 1:1) at 0° C. over 3hours. The reaction was judged to be complete when the pH stabilised at7 and the test for free amine (TLC) was negative. The reaction solutionwas rotary evaporated (at 40° C.) to reduce solvents. The product wasthen filtered off and vacuum dried at room temperature. The yield was70%.

TLC showed that the product was free of starting materials. The IRspectrum and elemental analysis results confirmed the authenticity ofthe product. The elemental analysis results are given in the followingtable.

    ______________________________________                                               Carbon     Hydrogen  Nitrogen                                          ______________________________________                                        Expected 33.42        1.72      11.99                                         Found    32.98        1.31      11.45                                         ______________________________________                                    

Characterisation of Products

The products were characterised using a combination of melting points,Infra-red [IR] spectra, elemental analyses and thin layer chromatography[TLC]. Melting points were determined on a Gallenkamp Melting PointApparatus. IR spectra were recorded on a Hitachi Model 260-10 InfraredSpectrophotometer and referred to Nujol mulls. Elemental analyses wereconducted (under contract) by the School of Chemistry, University of NewSouth Wales. TLC was carried out using Merck 60F₂₅₄ Silica Gel TLCfoils. A variety of eluents including acetone, water-saturated butanoland ethanol were used. The chromatograms were visualised at 254 nm witha Universal UV Lamp (CAMAG Muttenz Schweiz).

APPLICATION METHODS

1. Di-chloro-s-triazine UV absorber derivatives on cotton

Example 7

These compounds may be applied to cotton by either exhaustion or padmethods

A suitable exhaustion method is as follows:

Apply 2% owf absorber compound, 10% owf sodium chloride and 0.1% owfwetting agent (e.g. a nonylphenyl polyethoxylate); LR 30:1; for 30minutes at 30° C. Then add 5% owf sodium carbonate and run for 30minutes. Finally wash off and dry.

The title compounds fix to the cotton via covalent bonds and henceprovide a permanent increase in the SPF of the treated cotton fabric.

Example 8

A suitable pad-batch method is as follows:

Apply a solution containing 2% owf absorber compound, 5% owf sodiumcarbonate and 0,1% owf wetting agent (e.g. a nonylphenyl polyethoxylate)by padding to achieve a pick-up of 100%. The padded fabric is thenbatched (cold) overnight in a sealed plastic wrap. Finally wash off anddry.

The title compounds fix to the cotton via covalent bonds and henceprovide a permanent increase in the SPF of the treated cotton fabric.

Example 9

A suitable alternative pad-batch method is as follows:

Apply a solution containing 2% owf absorber compound, 5% owf sodiumcarbonate and 0.1% owf wetting agent (e.g. a nonylphenyl polyethoxylate)by padding to achieve a pick-up of 100%. The padded fabric is thensteamed for 30 minutes at 100°-105° C. to achieve fixation. Finally washoff and dry.

The title compounds fix to the cotton via covalent bonds and henceprovide a permanent increase in the SPF of the treated cotton fabric.

2. Di-fluoro-mono-chloro-pyrimidine UV absorber derivatives on wool

Example 10

These compounds may be applied to wool by either exhaustion or padmethods.

A suitable exhaustion method is as follows:

Apply 2% owf absorber compound, 10% owf sodium sulphate, 1.0% owf aceticacid and 0.1% owf wetting agent (e.g. a nonylphenyl polyethoxylate); LR30:1. Start at 40° C., raise to 70° C. over 20 minutes, hold at 70° C.for 30 minutes; then raise the temperature to the boil and boil for 15minutes. Finally wash off and dry.

The title compounds fix to the wool via covalent bonds and hence providea permanent increase in the SPF of the treated wool fabric.

Example 11

A suitable alternative pad-batch method is as follows:

Apply a solution containing 2% owf absorber compound, 5% owf urea and0.1% owf wetting agent (e.g. a nonylphenyl polyethoxylate) by padding toachieve a pick-up of 100%. The padded fabric is then steamed for 30minutes at 100°-105° C. to achieve fixation. Finally wash off and dry.

The title compounds fix to the wool via covalent bonds and hence providea permanent increase in the SPF of the treated wool fabric.

In each of the following examples, a substance was applied to a fabricof less than 200 g/m² and the resultant combination was tested to obtainmeasurements on the change in SPF, whether the combination exhibitedcolourfastness to washing and whether the combination exhibitedcolourfastness to light.

UVR and SPF Measurement Methods

The ultra-violet transmission (direct and diffuse) of the sample wasmeasured over the UVR spectral range of 290 to 380 nm using a Cary 3UVR-visible spectrophotometer fitted with an integrating sphereattachment. A Schott UG#11 filter was used to eliminate the effects offluorescence from the fluorescent whitening agents (FWA) (if any) in thesample.

The SPF's (sun protection factors) were estimated for 2 mm "off skin" bya method developed in a research project initiated by the LidcombeHospital Dermatology Center. The method is fully described in thepublication entitled: "A Comparative Study of Fabric Protection againstUltraviolet-Induced Erythema Determined by Spectrophotometric and HumanSkin Measurements", by S. W. Menzies, P. B. Lukins, G. E. Greenoak, P.J. Walker, M. T. Pailthorpe, J. M. Martin, S. K. David and K. E.Georgouras, Journal of Photodermatology, Photoimmunology andPhotomedicine, 1992: 8(4), 157-163.

The ultra-violet transmission data, and the calculated SPF's, weremeasured on the fabric in a dry relaxed state (i.e. not stretched).

The predicted SPF's are indicative of the SPF's to be found on humanskin.

Colourfastness to washing

The colourfastness to washing of the untreated fabrics and UVR absorbertreated fabrics was determined by the methods described in AS 2001.4.15"Determination of Colourfastness to Washing: Test A: Colourfastness toSimulated Hand Laundering in the Presence of Soap".

Colourfastness to Liqht

The colourfastness to light of the untreated and UVR absorber treatedfabrics was determined by the methods described in AS 2001.4.21"Determination of Colourfastness to Light using an Artificial LightSource (Mercury Vapour, Tungsten Filament, Internally Phosphor-CoatedLamp)". Exposures were conducted for a total of 858 hours (circa 35days) for which the ISO Blue Standard Rating was 7.

Details of all the chemicals mentioned in the specification areavailable from the indicated proprietor.

And extensive search of the literature and enquires made of textilechemical suppliers in Australia showed that there a very fewwater-soluble (or water-dispersable) UV absorbers commerciallyavailable.

There are no UV absorbers commercially available for cotton.

Ciba-Geigy market two UV absorbers:

CIBAFAST N, which is described as "an agent to protect polyamide fibresagainst detrimental effects of light and heat and to improve the lightfastness of dyeings of these fibres.

CIBAFAST W, which is described as "an agent to protect wool againstdetrimental effects of light and heat".

Sandoz market one UV absorber for polyester:

FADEX F LIQUID, which is used to improve the light fastness of dyeingsof polyester, particularly those used in automobile upholstery.

Neither manufacturer makes any claim in their technical literatureregarding the use of these products to increase the SPF of fibre orfabric.

Example 12

Cibafast W (CFW) on wool.

Cibafast W is applied according to the exhaustion method. Firstly, it isdissolved in a bath and the product (fabric/fibre) has a wetting agentapplied to it before it is inserted into the bath. The bath is boiledfor approximately 1 hour to enable the Cibafast W to enter thefabric/fibre.

Utilising the above method, it is noted that Cibafast W is not glued tothe fabric but instead enters the fibres of fabric and in effect isbonded to the fibres due to the affinity between Cibafast W and the woolfibres.

In all the following examples, the "blank dyed" samples referred to aresamples that have been put through the identical application processused for the relevant UVR absorber, but without the active agent (UVRabsorber). The "blank dyed" sample often exhibits an improved SPF dueprimarily to shrinkage effects incurred in the process.

Using the application method described above, the following results wereobtained.

The stated "Suggested SPF" is the mean SPF less the 95% confidence limitrounded down to the nearest multiple of five. Thus the suggested SPF isconservative.

                  TABLE 1                                                         ______________________________________                                                     SPF RESULTS                                                      FABRIC DETAILS                                                                             (8 Samples)   SUGGESTED SPF                                      ______________________________________                                        Control Wool  42 ± 12   25+                                                Repeat       34 ± 9     25+                                                Blank Dyed   64 ± 9     55+                                                Repeat        84 ± 30   50+                                                1% CFW       108 ± 19   85+                                                2% CFW       108 ± 20   85+                                                5% CFW       127 ± 26   100+                                               10% CFW      102 ± 18   80+                                                ______________________________________                                    

From Table 1 it is apparent that Cibafast W has caused a significantimprovement in the SPF ratings for this wool fabric. An application of1% CFW is sufficient to double the blank dyed SPF value.

The fastness of Cibafast W on wool to washing and light is given in thefollowing Table 2.

                  TABLE 2                                                         ______________________________________                                        FABRIC   INITIAL   SPF AFTER  SPF AFTER 858                                   DETAILS  SPF       WASHING    HOURS EXPOSURE                                  ______________________________________                                        Control Wool                                                                           36 ± 3  42 ± 18                                                                              59 ± 20                                               (30+)     (20+)      (35+)                                           Blank Dyed                                                                              84 ± 30                                                                              99 ± 29                                                                              135 ± 40                                              (50+)     (70+)      (95+)                                           1% CFW   130 ± 50                                                                             125 ± 34                                                                              198 ± 112                                             (80+)     (90+)      (85+)                                           2% CFW   174 ± 76                                                                             180 ± 85                                                                              147 ± 26                                              (95+)     (90+)      (100+)                                          ______________________________________                                    

From Table 2 it is apparent that the improved SPF ratings obtained byusing Cibafast W are "fast" to both washing and to light.

Example 13

Fadex F on Polyester

Method of Application

Fadex F was first applied to polyester at 100° C. in aGoodbrand-Jeffries Dyemaster machine (S/N 13011) Laboratory DyeingMachine. However, it was noted that polyester required an increasedtemperature in order to effectively be impregnated with Fadex F.Accordingly, Fadex F was applied at 130° C. in the Labortex "Rapid"Dyeing Machine Model #8. A person skilled in the art would be familiarwith such a method.

The results of impregnating polyester with Fadex F are provided in Table3.

                  TABLE 3                                                         ______________________________________                                                      SPF RESULTS                                                     FABRIC DETAILS                                                                              (4 Samples) SUGGESTED SPF                                       ______________________________________                                        Control PES   15 ± 1   10+                                                 Repeat        15 ± 2   10+                                                 Blank Dyed    18 ± 2   15+                                                 1% Fadex      39 ± 4   35+                                                 2% Fadex F    48 ± 7   40+                                                 5% Fadex F    47 ± 8   35+                                                 ______________________________________                                    

From Table 3 it is apparent that Fadex F causes a significantimprovement in the SPF ratings of polyester fabric.

Fadex F was then tested for fastness to washing and light.

                  TABLE 4                                                         ______________________________________                                                                        SPF AFTER 858                                 FABRIC               SPF AFTER  HOURS                                         DETAILS  INITIAL SPF WASHING    EXPOSURE                                      ______________________________________                                        Control PES                                                                            15 ± 1   15 ± 2  18 ± 4                                              (10+)       (10+)      (10+)                                         Blank Dyed                                                                             18 ± 2   19 ± 5  not tested                                             (15+)       (10+)                                                    1% Fadex F                                                                             39 ± 4   37 ± 3  38 ± 3                                              (35+)       (30+)      (30+)                                         2% Fadex F                                                                             48 ± 7   45 ± 4  49 ± 6                                              (40+)       (40+)      (40+)                                         5% Fadex F                                                                             47 ± 8   52 ± 7  44 ± 8                                              (35+)       (40+)      (35+)                                         ______________________________________                                    

From the data given in Table 4, it is apparent that the improved SPFratings endowed by Fadex F on polyester are fast to both washing andexposure to light.

Example 14

Fadex F on Nylon

Because a temperature of 130° C. was required for the application ofFadex F to polyester, Fadex F was applied to nylon at 130° C. centigradein the Labortex "Rapid" Dyeing Machine.

The results of the application of Fadex F to nylon at 130° C. centigradeindicated that the colour of the nylon was effected and accordingly, atemperature of 100° C. was then adopted.

The Fadex F was thus applied to nylon at 100° C. centigrade in theDyemaster Dyeing Machine and was applied at 1% and 2% treatment levels.The treated nylon samples were only slightly yellowish in hue after thetreatment. The results of the treatment of nylon with Fadex F are givenin Table 5.

                  TABLE 5                                                         ______________________________________                                                                          SPF AFTER                                   FABRIC                SPF AFTER   858 HOURS                                   DETAILS   INITIAL SPF WASHING     EXPOSURE                                    ______________________________________                                        Control Nylon                                                                           10 ± 3 (5+)                                                                            15 ± 1 (10+)                                                                           10 ± 2                                   Repeat     9 ± 1 (5+)           (5+)                                       Blank Dyed                                                                              16 ± 2 (10+)                                                                           14 ± 1 (10+)                                                                           14 ± 3                                                                     (10+)                                       1% Fadex F                                                                              29 ± 8 (20+)                                                                           28 ± 2 (25+)                                                                           21 ± 5                                                                     (15+)                                       2% Fadex F                                                                              29 ± 6 (20+)                                                                           31 ± 10  28 ± 6                                                         (20+)       (20+)                                       ______________________________________                                    

From Table 5 it can be seen that Fadex F significantly improves the SPFratings of the nylon fabric employed. In addition, the results indicatethat the improvement in SPF ratings caused by the addition of Fadex F isfast to both washing and exposure to light.

Example 15

Fadex F on 65/35

Fadex F was applied to 65/35 polyester/cotton fabric at 130° C. in theLabortex "Rapid" dyeing machine. The results are given in Table 6.

                  TABLE 6                                                         ______________________________________                                                     SPF RESULTS                                                      FABRIC DETAILS                                                                             (4 Samples)   SUGGESTED SPF                                      ______________________________________                                        Control PES/CO                                                                             15 ± 2     10+                                                Blank Dyed   15 ± 5     10+                                                1% Fadex     28 ± 6     20+                                                2% Fadex F   25 ± 5     20+                                                3% Fadex F   24 ± 4     20+                                                ______________________________________                                    

From Table 6 it is apparent that Fadex F causes a significantimprovement in the SPF ratings of this polyester/cotton fabric. TheFadex F treated fabric, were then assessed for fastness to washing andto light. The results are given in Table 7.

                  TABLE 7                                                         ______________________________________                                                                  SPF AFTER                                           FABRIC DETAILS                                                                              INITIAL SPF WASHING                                             ______________________________________                                        Control PES   15 ± 2   NOT TESTED                                                        (10+)                                                           Blank dyed    15 ± 5   15 ± 1                                                         (10+)       (10+)                                               1% FADEX F    68 ± 6   27 ± 5                                                         (20+)       (20+)                                               2% FADEX F    25 ± 5   26 ± 4                                                         (20+)       (20+)                                               3% FADEX F    24 ± 4   24 ± 4                                                         (20+)       (20+)                                               ______________________________________                                    

From Table 7 it is apparent that Fadex F when applied to 65/35polyester/cotton improves the SPF ratings and the SPF ratings are fastto washing. Additional experimentation also indicates that the SPFratings are fast to exposure to light with the SPF after 858 hoursexposure being maintained at 20+.

Example 16

Fadex F was also applied to secondary cellulose acetate and triacetateand as with nylon provided increases in SPF ratings similar to thoseprovided for nylon. The Dyemaster Dyeing Machine method of applicationwas also found to be suitable.

From the above experiments it is apparent that light weight materials ofless than 200 grams per square meter, such as nylon, wool and polyestercan be provided with significantly increased values of SPF protection bythe addition of either Cibafast W or Fadex F as previously outlined. Theresultant and combination of fibre material and UVR absorber is bothfast to washing and to exposure to light.

Both Cibafast W and Fadex F are UVR absorbers and have previously beenused to protect particular fibres against detrimental effects of lightand heat. From a vast number of different chemical substances it hasbeen found that Cibafast W and Fadex F increased the SPF rating of thepreviously mentioned fibres to which they were applied, and at the sametime avoided deleterious effects to the fibres. Other chemicalsubstances used, for example, Cibafast N (a registered trade name ofCIBA-GEIGY) not only failed to increase the SPF rating of the treatedfabric but in many cases adversely affected the colour of the fabric sothat it would be unsuitable for use commercially.

                  TABLE 8                                                         ______________________________________                                                     SPF RESULTS                                                      SAMPLE       (8 Samples) SUGGESTED SPF                                        ______________________________________                                        Untreated Fabric                                                                            9 ± 1    5+                                                  Blank Dyed   14 ± 2   10+                                                  1% Cibafast N                                                                              17 ± 1   15+                                                  2% Cibafast N                                                                              16 ± 2   10+                                                  ______________________________________                                    

Table 8 provides the results of applying Cibafast N to nylon using theDyemaster Laboratory Dyeing machine. From Table 8 it is apparent thatCibafast N did not significantly increase the SPF rating of the treatedfabric and experiments also revealed that the Cibafast N induced a"greenish" colour into the white nylon fabric.

Example 17

Application of Compound 1 on cotton

(Compound 1 is 2,4-difluoro-5-chloro-6-phenylamino pyrimidine)

Compound 1 was prepared by the condensation of aniline (Fluka) and2,4,6-trifluoro-5-chloropyrimidine (Sandoz) by the method of Example 2.

17(a) Compound 1 was applied to 3 g samples of a woven plain weavecotton fabric (145 g/m² : Charles Parsons, Sydney) by exhaustion fromethanol. The formulation was as follows:

    ______________________________________                                        1%        o.w.f. Compound 1                                                   LR:       30:1                                                                Temp:     20° C.                                                       Time:     10 minutes                                                          Cure:     Fan forced over; 90° C.; 15 minutes.                         Wash:     Thorough cold rinse; then hot rinse (60° C.)                 Dry:      Fan forced oven; 60° C.; 30 minutes.                         ______________________________________                                    

The results are summarized in the Table 9.

                  TABLE 9                                                         ______________________________________                                        SPF RESULTS FOR WOVEN FABRIC                                                                             SUGGESTED                                          SAMPLE DETAILS SPF RESULTS SPF                                                ______________________________________                                        100% cotton control (4)                                                                      28.0 ± 3.2                                                                             20+                                                1% Compound 1 (8)                                                                            51.3 ± 7.7                                                                             40+                                                ______________________________________                                    

These preliminary small scale experiments show that Compound 1 has thecapability of significantly increasing the SPF of this 100% cotton wovenfabric.

17(b) Compound 1 was applied to 3 g samples of a woven plain weavecotton fabric (145 g/m² : Charles Parsons, Sydney) by exhaustion fromaqueous emulsion. The formulation was as follows:

    ______________________________________                                        1%           o.w.f. Compound 1 (emulsion)                                     LR           40:1                                                             Temp:        Start at 40° C., Raise to 65° C.                                over 30 minutes; hold 30                                                      minutes; raise to 98° C., hold 30                                      minutes.                                                         Wash:        Thorough cold rinse; then hot                                                 rinse (60° C.)                                            Dry:         Fan forced oven; 60° C.; 30                                            minutes.                                                         ______________________________________                                    

The results are summarized in the Table 10.

                  TABLE 10                                                        ______________________________________                                        SPF RESULTS FOR WOVEN FABRIC                                                                             SUGGESTED                                          SAMPLE DETAILS SPF RESULTS SPF                                                ______________________________________                                        100% cotton control (4)                                                                      28.0 ± 3.2                                                                             20+                                                Blank Treated (4)                                                                            26.6 ± 2.7                                                                             20+                                                1% Compound 1 (8)                                                                            42.6 ± 8.5                                                                             35+                                                2% Compound 1 (4)                                                                            44.4 ± 4.9                                                                             35+                                                ______________________________________                                    

These small scale experiments show that Compound 1 has the capability ofsignificantly increase the SPF of this 100% cotton woven fabric.

UV-Transmission

The UV-transmission of a 5 g/l ethanolic solution of Compound 1 wasmeasured in a 5 mm quartz cell using a Cary 3 UV-Visiblespectrophotometer.

The results are given in FIG. 1.

It can be readily seen that Compound 1 begins to absorb strongly below340 nm; ie in the UVB region. Thus this type of compound absorbs thevery harmful UVB rays YET will not significantly interfere with thefunction of fluorescent whitening agents (FWA). Thus the treated cottonremains a full white.

On the basis of these results it can be seen that 1% o.w.f. Compound 1gives a very significant increase in the SPF of this 100% cotton fabric.

Example 18

Application of Compound 2 on Cotton

(Compound 2 is p-(2,4-dichloro-s-triazine-6-ylamino)-o-methyl-phenylsulphonic acid sodium salt)

In the following application recipe it has been assumed that Compound 2has been formulated as 100% reactive compound.

In the determination of wash-fastness of the treated fabric, soap wasreplace by 1 g/l of OMO (OMO is a trade mark of Unilever plc).

18(a) Compound 2 was applied to 5 g samples of woven plain weave 100%cotton fabric (145 g/m² : Charles Parsons, Sydney) by exhaustion in aGoodbrand-Jeffries Laboratory Dyeing Machine. The formulation was asfollows:

    ______________________________________                                        50 g/l Sodium chloride (NaCl)                                                 ______________________________________                                        x %            o.w.f. Compound 2                                              LR             40:1                                                           Temp:          50° C.                                                  Time:          30 minutes                                                     Then:          Add 5 g/l Sodium carbonate                                     Run:           30 minutes of 50° C.                                    Wash:          Thorough cold rinse; then                                                     hot rinse (60° C.)                                      Dry:           Fan forced over; 60° C.; 60                                            minutes.                                                       ______________________________________                                    

The results are summarized in the Table 11.

                  TABLE 11                                                        ______________________________________                                        SPF RESULTS FOR WOVEN FABRIC                                                                             SUGGESTED                                          SAMPLE DETAILS SPF RESULT  SPF                                                ______________________________________                                        100% cotton control (4)                                                                      29.5 ± 2.6                                                                             25+                                                Blank treated sample (4)                                                                     26.4 ± 7.3                                                                             15+                                                1% Compound 2 (8)                                                                            41.1 ± 5.6                                                                             35+                                                2% Compound 2 (8)                                                                             47.7 ± 11.8                                                                           35+                                                ______________________________________                                    

These preliminary small scale experiments show that Compound 2 has thecapability of significantly increasing the SPF of this 100% cotton wovenfabric.

18(b) Winch Application

3% Compound 2 was applied to 600 g of a woven plain weave 100% cottonfabric (Charles Parsons, Sydney) by exhaustion in a laboratory scalewinch dyeing machine. The formulation was as follows:

    ______________________________________                                        50 g/l Sodium chloride (NaCl)                                                 ______________________________________                                        3%             o.w.f. Compound 2                                              LR             30:1                                                           Temp:          50° C.                                                  Time:          30 minutes                                                     Then:          Add 5 g/l Sodium carbonate                                     Run:           30 minutes of 50° C.                                    Wash:          Thorough cold rinse; then                                                     hot rinse (60° C.)                                      Dry:           Tumble dry: 60° C.; 60                                                 minutes.                                                       ______________________________________                                    

The results are summarized in the Table 12.

                  TABLE 12                                                        ______________________________________                                        SPF RESULTS FOR WOVEN FABRIC                                                                             SUGGESTED                                          SAMPLE DETAILS SPF RESULT  SPF                                                ______________________________________                                        100% cotton control (8)                                                                      24.5 ± 3.6                                                                             20+                                                3% Compound 2 (8)                                                                            41.0 ± 4.4                                                                             35+                                                ______________________________________                                    

These which dyeing experiments show that Compound 2 has significantlyincreased the SPF of this 100% cotton woven fabric.

The fastness to washing and to light of the Compound 2 (winch) treated100% cotton was then evaluated and the results are given in Table 13.

                  TABLE 13                                                        ______________________________________                                        FASTNESS RESULTS                                                                                           SUGGESTED                                        SAMPLE DETAILS   SPF RESULT  SPF                                              ______________________________________                                        100% cotton control (8)                                                                        24.5 ± 3.6                                                                             20+                                              3% Compound 2 (8)                                                                              41.0 ± 4.4                                                                             35+                                              After 1 wash/drying cycle (8)                                                                  39.9 ± 4.5                                                                             35+                                              After 5 wash/drying cycle (8)                                                                  41.8 ± 3.6                                                                             35+                                              After 70 hours light exposure                                                 Blank (Untreated) (8)                                                                          32.1 ± 5.3                                                                             25+                                              Treated (8)       50.1 ± 12.2                                                                           35+                                              After 162 hours light                                                                          43.0 ± 5.8                                                                             35+                                              (8)                                                                           exposure                                                                      ______________________________________                                    

18(c) Pad-Batch Application to knitted fabric

3% Compound 2 was applied to circa 35 g of a knitted 100% cotton fabric(Avon 100% cotton; Size XXL; Sunsafe 30+ : This fabric would have aweight of 180-190 g/cm²) by padding using a laboratory scale paddingmachine. The formulation was as follows:

    ______________________________________                                        3%              w/w Comuound 2                                                                5 g/l sodium carbonate                                        Add-on:         90%                                                           Temp:           Room temperature                                              Batch:          6 hours (cold) in sealed                                                      plastic bags                                                  Wash:           Thorough cold rinse;                                                          then hot rinse (60° C.)                                Dry:            Tumble dry: 60° C.; 60                                                 minutes.                                                      ______________________________________                                    

The results are summarized in the Table 14.

                  TABLE 14                                                        ______________________________________                                        PAD - BATCH RESULTS ON KNITTED FABRIC                                                                    SUGGESTED                                          SAMPLE DETAILS SPF RESULT  SPF                                                ______________________________________                                        100% cotton control (8)                                                                      33.7 ± 5.7                                                                             25+                                                Blank padded sample (8)                                                                      51.5 ± 4.5                                                                             45+                                                2.7% Compound 2                                                                              103.1 ± 17.0                                                                           85+                                                (8)                                                                           ______________________________________                                    

The "blank" padded sample has shrunk, giving rise to the higher SPF ofthis specimen. The Compound 2 treated sample has a greatly improved SPFover both the control and blank samples.

These pad-batch dyeing experiments show that Compound 2 hassignificantly increased the SPF of the 100% cotton knitted fabric.

18(d) Pad-Batch Application to woven fabric

3% Compound 2 was applied to circa 25 g of a woven 100% cotton fabric(Charles Parsons) by padding using a laboratory scale padding machine.the formulation was as follows:

    ______________________________________                                        3%              w/w Comuound 2                                                                5 g/l sodium carbonate                                        Add-on:         90% (Hence 2.7% applied)                                      Temp:           Room temperature                                              Batch:          6 hours (cold) in sealed                                                      plastic bags                                                  Wash:           Thorough cold rinse;                                                          then hot rinse (60° C.)                                Dry:            Tumble dry: 60° C.; 60                                                 minutes.                                                      ______________________________________                                    

The results are summarized in the Table 15.

                  TABLE 15                                                        ______________________________________                                        SPF RESULTS FOR PADDED WOVEN FABRIC                                                                      SUGGESTED                                          SAMPLE DETAILS SPF RESULT  SPF                                                ______________________________________                                        100% cotton control (8)                                                                      24.5 ± 3.6                                                                             20+                                                Blank padded woven (8)                                                                       30.9 ± 4.5                                                                             25+                                                2.7% Compound 2                                                                              59.5 ± 6.9                                                                             50+                                                (8)                                                                           ______________________________________                                    

These pad-batch dyeing experiments show that Compound 2 hassignificantly increased to SPF of this 100% cotton woven fabric.

On the basis of these results it can be seen that Compound 2 can beconveniently applied to cotton fabrics (either knitted or woven) by both"exhaustion" and "pad-batch" methods.

The treated fabrics are fast to both washing and to light.

The treated fabrics have significantly higher SPFs than the controlfabrics (and blank treated fabrics).

Compound 2 beings to absorb strongly below 359 nm, ie in the UVB region.UVB is most damaging to the skin and the principal cause of skin cancer.

By not absorbing significantly above 350 nm, Compound 2 does not inhibitthe function of fluorescent whitening agents (FWA) and hence the fabricremains a bright white yet has a high SPF.

We claim:
 1. A method of increasing the SPF rating of cellulosic orprotein fiber or fabric, comprising applying, by exhaustion orpad-methods, to said cellulosic or protein fiber or fabric one or moreUVR absorber compounds of formulae (III) or (IV): ##STR5## wherein A is--NH-- or --SO₂ -- and when A is --NH--, B is selected from a compoundof formulae (i)-(vii) as follows: ##STR6## and when A is --SO₂ --, B isselected from a compound of formulae (viii)-(x) as follows:(viii)--CH═CH--OSO₃ H (ix) --CH₂ --CH₂ --OSO₃ H (x) --NH--CH₂ --CH₂ --OSO₃ H;Ris independently selected from --OH, --NH₂, --SO₃ M⁺, --SO₃ H, alkyl,alkoxy, alkanoyl, alkylcarboxylate, --S-alkyl, --CF₃, and --N-di-alkyl;n=0, 1, 2, 3, or 4; M⁺ =cation; X=is independently selected from H, Cl,F, or Br; and Y=X or R.
 2. A method of claim 1 wherein said cellulosicor protein fiber or fabric has a density of less than 200 g/m² wherebyan application of less than 3% (based on weight of fiber or fabric) of acompound of formulae (III) or (IV) produces an SPF rating of greaterthan
 20. 3. A method of claim 2 wherein an application of less than 2%of a compound of formula (III) or (IV) produces an SPF rating of greaterthan
 20. 4. A method of claim 1 wherein said cellulosic or protein fiberis cotton and wherein said method comprises applying a compound offormula (IV) where A is --NH--, B is a compound of formula (ii), X isCl, n is 2 and one R is in the 3-position of the phenyl ring and is--CH₃ and the other R is in the 4-position and is --SO₃ --Na⁺.
 5. Anarticle of clothing comprising a plurality of fibers and one or more UVRabsorber compounds, wherein the plurality of fibers have a density ofless than 200 grams per square meter and the SPF rating of the articlehas been increased to at least 20 by the addition of less than 3% (basedon weight of fiber) of one or more UVR absorber compounds of formulae(III) or (IV): ##STR7## wherein A is --NH-- or --SO₂ -- and when A is--NH--, B is selected from a compound of formulae (i)-(vii) as follows:##STR8## and when A is --SO₂ --, B is selected from a compound offormulae (viii)-(x) as follows:(viii) --CH═CH--OSO₃ H (ix) --CH₂ --CH₂--OSO₃ H (x) --NH--CH₂ --CH₂ --OSO₃ H;R is independently selected from--OH, --NH₂, --SO₃ M⁺, --SO₃ H, alkyl, alkoxy, alkanoyl,alkylcarboxylate, --S-alkyl, --CF₃, and --N-di-alkyl; n=0, 1, 2, 3, or4; M⁺ =cation; X=is independently selected from H, Cl, F, or Br; and Y=Xor R.
 6. An article of clothing of claim 5, wherein the SPF rating ofthe article has been increased to at least 20 by the addition of lessthan 2% UVR absorber.
 7. An article of clothing comprising a pluralityof fibers and one or more UVR absorber compounds of formulae (III) or(IV): ##STR9## wherein A is --NH-- or --SO₂ -- and when A is --NH--, Bis selected from a compound of formulae (i)-(vii) as follows: ##STR10##and when A is --SO₂ --, B is selected from a compound of formulae(viii)-(x) as follows:(viii) --CH═CH--OSO₃ H (ix) --CH₂ --CH₂ --OSO₃ H(x) --NH--CH₂ --CH₂ --OSO₃ H;R is independently selected from --OH,--NH₂, --SO₃ M⁺, --SO₃ H, alkyl, alkoxy, alkanoyl, alkylcarboxylate,--S-alkyl, --CF₃, and --N-di-alkyl; n=0, 1, 2, 3, or 4; M⁺ =cation; X=isindependently selected from H, Cl, F, or Br; and Y=X or R.
 8. Clothingor fabric in which the SPF rating has been increased to 20 or moreprepared by a method which comprises applying, by exhaustion orpad-methods, to clothing or fabric one or more UVR absorber compounds offormulae (III) or (IV): ##STR11## wherein A is --NH-- or --SO₂ -- andwhen A is --NH--, B is selected from a compound of formulae (i)-(vii) asfollows: ##STR12## and when A is --SO₂ --, B is selected from a compoundof formulae (viii)-(x) as follows:(viii) --CH═CH--OSO₂ H (ix) --CH₂--CH₂ --OSO₃ H (x) --NH--CH₂ --CH₂ --OSO₃ H;R is independently selectedfrom --OH, --NH₂, --SO₃ M⁺, --SO₃ H, alkyl, alkoxy, alkanoyl,alkylcarboxylate, --S-alkyl, --CF₃, and --N-di-alkyl; n=0, 1, 2, 3, or4; M⁺ =cation; X=is independently selected from H, Cl, F, or Br; and Y=Xor R.